Method of forming a meat curing brine

ABSTRACT

A subtantially dry, free-flowing particulated mixture suitable for use in the &#34;dry&#34; and &#34;wet&#34; curing of meat products, such as bacon, and for suppression of N-nitrosamine formation during subsequent cooking of the cured meat products comprising a substantially uniform mixture of water soluble particulated meat curing constituents, water insoluble amorphous absorbent silica particles and a liquid alpha-tocopherol uniformly distributed on the water soluble particles and said silica particles. The mixture preferably further contains particulated lecithin, when it is to be employed for &#34;wet&#34; curing, to further enhance the stability of the aqueous brine solution produced by dissolving the free-flowing mixture in water, through which the alpha-tocopherol is uniformly dispersed, providing a pumpable liquid for injection into meat products. The free-flowing mixture can contain appropriate amounts of any one or mixtures of other ingredients of the types conventionally employed in the curing of meat products, such as salt, sugar, erythorbates, ascorbates, phosphate salts, nitrites, nitrates and the like.

This is a division of application Ser. No. 358,629, filed Mar. 16, 1982,U.S. Pat. No. 4,434,187.

BACKGROUND OF THE INVENTION

It is a well-known practice to add sodium nitrite to meat products,particularly bacon, to improve the quality and taste and to furtherinhibit the growth of deadly botulinal toxin during storage of the meatprior to consumption. Approximately ten years ago, it was discoveredthat during the cooking of such nitrite-containing meat products,N-nitrosamines such a N-nitrosopyrrolidine (NPYR) andN-nitrosodimethylamine (NDMA) were formed as a result of chemicalreactions between certain classes of amines comprising naturalcomponents of such foods and the nitrite additive used in the curing andpreservation of the meat product. Such N-nitrosamines have now beenshown to be carcinogens in animals and considerable work has beenconducted to suppress or inhibit the formation of such N-nitrosaminesduring the cooking or frying stage of such meat products.

Recently, it has been discovered that dl-alpha-tocopherol (Vitamin E),when incorporated in such meat products prior to cooking is effective insuppressing the formation of N-nitrosamines. The dl-alpha-tocopherolemployed is in the form of a water insoluble viscous liquid which hasbeen employed in the so-called "dry curing" of meat products by directapplication to the surface of the meat to which the meat curingadditives are also added, such as the curing salt, nitrites, and otherconventional curing additives. This method of dry curing meat productshas the disadvantage of requiring lengthy time period of up to about twoweeks to penetrate the meat product and the distribution of the cure andliquid tocopherol additive is less than uniform. For these reasons, over90 percent of bacon is cured employing the so-called "wet curing"process in which a brine solution or "curing pickle" incorporating thecuring additives and, experimentally, the alpha-tocopherol agent isinjected at various locations into pork bellies employing tubularneedles whereby a more rapid cure and more uniform distribution of thecuring agent is attained.

A continuing problem associated with such wet curing or "pump"techniques is the difficulty of incorporating and maintaining thealpha-tocopherol in a curing pickle in a uniform dispersed condition dueto its hydrophobic characteristics necessitating the use of relativelyhigh concentrations of emulsifying agents. For example, 200 ppm ofpolysorbate 60 or 80 are required in the brine solution to retainpumpability thereof. Such high levels of synthetic emulsifying agentsrequired and the tendency of such brine solutions to become unstableresulting in segregation and/or agglomeration of the alpha-tocopheroladditive has detracted somewhat from the efficient use of suchsolutions.

A further problem associated with both the dry and wet curing systemshas been the difficulty of providing an alpha-tocopherol containingcuring material which is uniform and free flowing enabling uniformdistribution of the material directly on the surface of the meatproducts to be cured or in the continuous feeding of such a mixture to abrine tank for replenishment of the brine solution as it is consumed.

The present invention overcomes many of the problems and disadvantagesassociated with prior art compositions and techniques by providing asubstantially dry free-flowing particulate mixture which is stable instorage and can effectively be employed in both the dry curing and wetcuring methods and which upon dissolution forms a brine solution inwhich the alpha-tocopherol is substantially uniformly distributed in thepresence of only moderate agitation, assuring pumpability of the brinecuring solution and uniform distribution of the additive ingredientstherein throughout the meat product.

SUMMARY OF THE INVENTION

The benefits and advantages of the present invention are based on thediscovery that substantially uniform free-flowing particulate curingcompositions containing effective amounts of dl-alpha-tocopherol can beprepared suitable for use in dry curing of meat products and which arealso suitable for forming a curing brine or curing pickle for use in thewet or pump cure method in which the alpha-tocopherol is substantiallyuniformly dispersed and remains stable by virtue of the incorporation ofcontrolled amounts of water soluble finely particulated curingconstituents in combination with finely particulated, aqueous insoluble,amorphous, absorbent, silica particles. The alpha-tocopherol constituentis released by the water soluble particles and silica particles upon drysurface application to the meat or is dispersed into brine upondissolution of the particulated mixture into water, and said curingpickle is injected into the meat product attaining a substantiallyuniform distribution of the tocopherol constituent whereby a significantsuppression in N-nitrosamine production is attained during thesubsequent cooking or frying of the cured meat product. The specificquantity of water soluble particulated curing constituents, silicaparticles and alpha-tocopherol employed in the mixture is dictated tosome extent by federal regulations regarding permissible levels of flowagents in free-flowing salt mixtures, the quantity of nitrite and/ornitrate salts employed in the curing mixture, the level of tocopherolpermitted, the level of N-nitrosamine permissible, and the strength ofthe curing brine solution desired. Accordingly, in accordance with thecomposition aspects of the present invention, the mixture contains asits essential constituents controlled amounts of water solubleparticulated curing constituents such as salt, sugar, phosphates, curingaccelerators and the like; amorphous porous silica particles anddl-alpha-tocopherol. Optionally and preferably, the free-flowingparticulated mixture may further contain a finely particulated lecithinto synergistically enhance the stability of the dispersion of themixture following dissolution in water to form a curing brine.

In accordance with the process aspects of the present invention, thesubstantially dry, free-flowing mixture is prepared by applying to afinely particulated water soluble curing constituent or mixture ofconstituents, controlled at a temperature of about 100° to about 140°F., an appropriate amount of dl-alpha-tocopherol in liquid form andblending the two constituents until a uniform distribution of thetocopherol on the surfaces of the particles is attained. Thereafter, thefinely particulated silica particles are added to the mixture withcontinued blending to form a substantially uniform mixture. Inaccordance with an optional practice, a controlled amount of a finelyparticulated lecithin is thereafter added at a temperature below themelting point of the lecithin additive followed by further blending toeffect uniform distribution. When lecithin is employed as an optionalbut preferred addition agent, it can be added to the mixture prior to orafter the addition of the silica particles. It is also contemplated thatnitrite/nitrate salts can be blended into the mixture if they areencapsulated or if appropriate packaging safeguards are employed toavoid nitrite/nitrate decomposition or in the event the mixture is to beused shortly after preparation. Any of the remaining water solublecuring constituents such as salt, sugar, phosphate salts, erythorbates,ascorbates and the like can be added thereafter and blended to achieveuniformity of the mixture.

In accordance with a further method aspect of the present invention, thesubstantially dry free-flowing mixture can be applied directly to thesurface of meat products along with other curing constituents, if notalready incorporated in the mixture, to effect a dry curing thereof, oralternatively, can be dispersed in water or a brine solution to form anaqueous brine dispersion in which the alpha-tocopherol additive issubstantially uniformly distributed and which is pumpable and can beinjected by the wet curing method into such meat products. Thefree-flowing nature of the mixture enables use of automatic feedingequipment for effecting continuous replenishment of the brine curingtank during such wet curing operations.

Additional benefits and advantages of the present invention will becomeapparent upon a reading of the Description of the Preferred Embodimentsconsidered in conjunction with the specific examples provided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the composition aspects of the present invention, thesubstantially dry, free-flowing particulated mixture contains controlledeffective amounts of a water soluble particulated curing constituent ormixtures thereof, aqueous insoluble, amorphous, tocopherol absorbent,silica particles and dl-alpha-tocopherol substantially uniformlydistributed on the water soluble particulated curing constituents anddistributed on and absorbed in said silica particles.

The water soluble particulated meat curing constituents or mixture ofconstituents comprises materials selected from the group includingsodium chloride, potassium chloride, mixtures of the foregoing as wellas substances acceptable for use in the preparation and/or cure of meatproducts as specifically enumerated in 9CFR 318.7, the substance ofwhich is also incorporated herein by reference including futureadditions and deletions thereof. Most common substances employed in thecuring of meat products in addition to salt are phosphates andpolyphosphates, sugars, ascorbates, erythorbates, alkali metal nitritesand/or nitrates, and the like. The most common water solubleparticulated constituent is sodium chloride, potassium chloride andmixtures thereof. The particulated curing constituents are of a foodgrade as defined in "Food Chemicals Codex" Third Edition, 1981 byNational Academy Press, Washington, D.C.

The specific configuration of the particles of water soluble curingconstituents is not critical in attaining the benefits of the presentinvention. For example, sodium chloride can be granulated, dendritic,flake shape and the like. Particularly satisfactory results are obtainedemploying natural flake salt particles produced by the Alberger process.The average particle size of the water soluble curing constituents isgenerally controlled to less than about 500 microns with averageparticle size ranges of from about 100 to about 300 microns beingpreferred. The moisture content of the particulated curing constituentsis preferably as low as possible with surface moisture contents of lessthan about 2 percent by weight, preferably 0.1 percent by weight or lessbeing particularly satisfactory.

The dl-alpha-tocopherol additive agent is employed in the form of aviscous liquid comprising either a substantially puredl-alpha-tocopherol or a commercial mixture containing other isomers inwhich the dl-alpha-tocopherol constitutes the major active constituent.The tocopherol additive can be employed in amounts up to about 5 percentby weight of the total mixture with amounts ranging from about 0.3 toabout 4 percent being preferred and with amounts of from about 1.5 toabout 3.5 percent being typical.

The finely particulated amorphous, porous and absorbent silica particlesare of an average particle size ranging from about 0.5 up to about 9microns, with average particle sizes of from about 1.5 to about 7microns usually being preferred. While the concentration of the silicaparticles is usually dictated in consideration of the water-solublecuring constituents and the quantity of tocopherol additive employed,concentrations as high as about 3 percent by weight in the mixture canbe employed. However, in view of current federal regulations dictating amaximum concentration of silica flow agents in dry particulated saltmixtures at a maximum level of 2 percent, the concentration of thesilica particles is generally controlled at a level of 2 percent byweight to levels as low as about 1 percent by weight. When the powdermixture is to be employed for forming a pumpable brine solution for wetcuring meat products, it is generally preferred to control the weightratio of silica particles to tocopherol at a level of at least about0.33 parts silica particles per part by weight tocopherol in order toattain a substantially PG,12 free flowing dry mixture and in addition, asubstantially stable dispersion of the alpha-tocopherol in an aqueoussolution.

The particular concentration of the dl-alpha-tocopherol employed is alsoin part dictated by federal regulations and in further consideration ofthe nitrite/nitrate salts employed in the curing process and the desiredlevel of suppression of N-nitrosamines desired in the cooked meatproducts. In accordance with current federal standards, concentrationsof nitrosamines in cooked meat products of greater than 16 parts perbillion (ppb) are cause for retention of product; 10-16 ppb areconsidered an actionable level for investigation and process evaluation;levels less than 10 ppb are acceptable for distribution and consumption,with no detectable nitrosamines being preferred. Tests conductedemploying the present composition in the wet cure of pork bellies hasevidenced a suppression of N-nitrosamines to a level of as low as about2 ppb in cooked-out bacon. Federal regulations have also tentativelyestablished a maximum concentration of dl-alpha-tocopherol based on thefresh weight of a pork belly at a maximum level of 500 ppm. Thislimitation in further combination with a further federal regulation thata maximum of about 10 percent weight increase in the original fresh meatproduct is permitted by the addition of water and curing additivesdictates the use of a particulated mixture of the present inventioncontaining an appropriate percent of alpha-tocopherol to attain about a10 percent weight increase in the original fresh meat treated to providea maximum of 500 ppm concentration of alpha-tocopherol on the basis ofthe fresh meat product.

For example, a particulated mixture incorporating sodium chloride as thewater soluble particulated curing constituent in an amount to produce a15 percent sodium chloride brine solution will contain about 3.33percent of alpha-tocopherol, based on the salt weight, to attain a 10percent weight increase of the fresh meat to provide a 500 ppmconcentration of said alpha-tocopherol. Typically, curing brines orpickles are used ranging from about 10 to about 20 percent by weightsodium and/or potassium chloride with concentrations of about 12 to 18percent being usual. At a brine concentration of about 10 percent salt,the alpha-tocopherol content in the dry particulated mixture would beabout 4.33 percent while at a brine concentration of about 20 percent,the alpha-tocopherol content in the dry mixture would be about 2.17percent to provide a 500 ppm tocopherol concentration in the pumped meatproduct.

Similarly, when the particulated curing agent is sodium chloride, thesilica constituent, because of federal regulations, is controlled at amaximum level of 2 percent by weight of the sodium chloride. The dryparticulated mixture, accordingly, contains typically 3.25 percent byweight alpha-tocopherol, 1.90 percent by weight of the finelyparticulated silica particles and 94.85 percent by weight of sodiumchloride particles.

When the water soluble particulated curing constituent comprisessubstances other than sodium and/or potassium chloride, such as sugar,phosphates and polyphosphates, ascorbates, erythorborates, nitritesand/or nitrates as well as mixtures of the foregoing, then the silicaparticles can be present in an amount of up to about 1 percent to about4 percent by weight with the alpha-tocopherol being present at a weightratio of silica particles to tocopherol of at least about 0.33 partsilica particles per part by weight tocopherol to attain a free-flowingsubstantially dry mixture and a substantially stable dispersion uponformation of the aqueous solution.

The aqueous insoluble, porous, amorphous, absorbent silica particles cancomprise silica gel or hydrated silicon dioxide particles which servethe dual function of a flow agent for the dry powder mixture,facilitating uniform distribution of the tocopherol additive in a drycuring process, as well as for providing an unexpected improvement inthe stability of the dispersion of the tocopherol when the dry powderedmixture is dissolved to form a brine solution for use in wet curingprocesses. Silica materials which are commercially available and havebeen found particularly satisfactory for this purpose include a silicagel sold under the brand name Syloid 244 available from W. R. Grace &Company; hydrated silicon dioxide particles sold under the branddesignations Zeothix 265 and Zeofree 80 available from J. M. HuberCorporation.

The silica gel material is conventionally produced by the acidificationof a soluble silicate solution producing a hydrosol which later forms acontinuous silica hydrogel or a gelatinous precipitate depending on theconcentration, degree of neutralization, and method of mixing. Usually,the final gel is obtained by washing the hydrogel to free it ofelectrolytes and drying to such an extent that the resulting gel isessentially free of water. The Syloid 244 material comprises a silicagel and is of an average particle size of 4 microns, a surface area ofabout 310 square meters per gram, an oil absorption of about 305 cubiccentimeters per 100 grams, a bulk density of about 7 pounds per cubicfoot and a pore diameter of about 150 Angstroms.

The hydrated silicon dioxide particles suitable for use in accordancewith the present invention are also referred to as precipitated silicaswhich are formed by the destabilization of soluble silicates, usually byacid neutralization. The destabilization is carried out in a solutionwhich also contains polymerization inhibitors, such as inorganic salts,which cause an extremely fine precipitate of hydrated silica to beformed. The precipitate is thereafter filtered, washed essentially freeof occluded salts and thereafter dried to the desired degree. TheZeothix 265 material comprising a hydrated or precipitated silica is ofan average particle size of about 1.5 to about 2 microns, a surface areaof from about 200 to about 300 square meters per gram, an oil absorptionof about 200 to about 240 cubic centimeters per 100 grams, and a bulkdensity of about 5 to about 7 pounds per cubic foot. The Zeofree 80material has an average particle size of about 5 to about 7 microns, asurface area of about 120 to about 150 square meters per gram, an oilabsorption of about 180 to about 200 cubic centimeters per 100 grams,and a bulk density of about 10 to about 12 pounds per cubic foot.

The aqueous insoluble silica particles suitable for use in the practiceof the present invention are characterized as having an average particlesize ranging from about 0.5 to about 9 microns, preferably about 1.5 toabout 7 microns; a surface area of about 100 to about 500, preferably120 to about 310 square meters per gram; an oil absorption of about 100to about 350, preferably 180 to about 305 cubic centimeters per 100grams; a bulk density of from about 3 to about 15, preferably about 5 toabout 12 pounds per cubic foot, and an average pore diameter of about 20to about 300 angstroms; preferably about 100 to about 200 Angstroms.

In addition to the foregoing essential constituents, the dry particulatemixture can optionally further contain up to about 10 percent by weight,and preferably from about 1 percent to about 4 percent by weight of asubstantially purified or a finely particulated lecithin tosynergistically assist in the dispersion of the alpha-tocopheroladditive in the brine solution for wet curing processes. The quantity ofthe lecithin is employed in consideration of the concentration of thealpha-tocopherol present in relationship to the silica particles presentand typically is employed in an amount to provide a weight ratio oflecithin to silica particles of about 6:1 to about 0.5:1, preferablyabout 3:1 to about 0.8:1. For cost considerations, commercial lecithinmaterials can be employed for this purpose containing at least 50percent by weight of acetone-insoluble phosphatides, but preferably over90 percent acetone-insoluble phosphatides are employed.

It is also contemplated that appropriate amounts of nitrite and/ornitrate salts can be incorporated in the mixture in proportionsconventionally employed for the curing of meat products. When used, itis preferred that such nitrite and/or nitrate salts compriseencapsulated or stabilized materials which can be used in the mixturewithout deterioration. Suitable encapsulated or stabilized nitriteand/or nitrate salts are described in U.S. Pat. Nos. 2,145,417,2,668,771 and 3,052,560 the teachings of which are incorporated hereinby reference. In the event non-stabilized nitrite and/or nitratematerials are used in the mixture, it is usually necessary, if thecuring mixture is not used shortly after preparation, to vacuum packagethe blended mixture and backfill the package with an inert gas such asnitrogen in order to prolong the stability and useful life of themixture.

The preparation of the free-flowing particulated mixture is preferablyperformed by introducing a measured quantity of the water-solubleparticulated curing constituents at a moderate temperature of about 100°to about 140° F. into a suitable mixing or blending apparatus such as aribbon blender. Thereafter, during constant agitation, thealpha-tocopherol additive is added and further mixing is continued untilthe tocopherol is uniformly distributed as a film over substantially allof the surfaces of the particles. Thereafter the particulated silicaflow agent is added during continued further mixing for a period of timeto effect a uniform mixture of good flowability and a partial coating ofthe silica particles with the tocopherol additive. If the optionallecithin additive agent is to be employed, it is preferably introducedin the form of a dry powder and the mixture is controlled at atemperature preferably below the melting point of the lecithinconstituent to avoid melting thereof and inhibiting the free flowingcharacteristics of the particulated mixture. After the further mixing ofthe lecithin constituent, the other optional curing additives are addedand blended for an additional time to produce a substantially uniformblend.

Although the sodium nitrite constituent is usually excluded from themixture for the reasons hereinabove set forth, when employed, it can bedirectly introduced during mixing when proper precautions are taken inthe blending and packaging operation.

The dry particulated mixture containing all of the additives necessaryfor curing meat products or the mixture containing the essential andcertain optional constituents in further combination with a supplementalmixture of the remaining constituents can be directly applied bysprinkling and rubbing to the surfaces of the meat product in accordancewith the conventional dry curing process. Alternatively, the mixture canbe dispersed in water to form a curing brine nominally containing about12 to about 18 percent by weight sodium chloride, effecting asubstantially uniform distribution of the alpha-tocopherol constituentand the silica flow agent in the form of a substantially stabledispersion, in further combination with appropriate quantities of theremaining curing agents for pumping into pork bellies and other meatproducts by needle injection to produce a weight increase of the meatproduct up to about 10 percent of its original weight and providing amaximum concentration of alpha-tocopherol of about 500 ppm.

In order to further illustrate the composition and process aspects ofthe present invention, the following examples are provided. It will beunderstood that the examples are provided for illustrative purposes andare not intended to be limiting of the scope of the present invention asherein described and as set forth in the subjoined claims.

EXAMPLE 1

A substantially dry, free-flowing particulated mixture is preparedcontaining 1000 grams of Alberger fine flake salt, 33.3 gramsalpha-tocopherol, 66.6 grams of powdered lecithin and 20.0 grams of anamorphous porous silica powder. The Alberger fine flake salt is of ahigh purity, food grade sodium chloride of a mesh size ranging from 40to 100 U.S. standard sieve series having a surface area of 64.5 squarefoot per pound and a bulk density of about 49 to 58 pounds per cubicfoot. The alpha-tocopherol constituent is a product commerciallyavailable under the designation dl-alpha tocopherol available from RocheChemical Division, Hoffmann-LaRoche, Inc., Belvidere, N.J. The lecithinadditive comprises a commercially available product sold under the branddesignation M-C-THIN PUR available from Food Ingredients, Inc. of ElkGrove Village, Ill. The silica flow agent constituent comprises amaterial as previously described sold under the brand designation Syloid244 available from W. R. Grace & Company.

A uniform mixture of the constituents is prepared by introducing thesodium chloride fine flake salt into a ribbon blender at a moderatetemperature of about 120° F. and to which the alpha-tocopherol is addedduring continued further mixing for a period of two minutes. Thereafter,the silica additive flow agent is added during continued further mixingfor a five minute period. The finely powdered lecithin additive isthereafter added during further mixing of one minute with the saltmixture at a temperature of less than about 120° F.

The resultant mixture is substantially dry and free flowing with theconstituents uniformly distributed therethrough.

EXAMPLE 2

A substantially dry free-flowing powder mixture is prepared containing1,000 grams fine flake salt, 33.3 grams alpha-tocopherol, 36.7 gramssodium ascorbate, 553.3 grams fine cane sugar, 233.3 grams sodiumtripolyphosphate, 33.3 grams lecithin and 20 grams of the silica flowagent.

The sodium chloride salt, alpha-tocopherol, lecithin and silica additiveagents are the same as those employed in Example 1.

The uniform mixture is prepared by the addition of sodium chloride saltat a temperature of about 120° F. to a ribbon blender and to which thealpha-tocopherol is added during continued further mixing for a periodof two minutes. The silica flow agent is thereafter added followed byfurther mixing for a period of four minutes whereafter the lecithinpowder is added following an additional one minute mix. At thecompletion of the preliminary blending, the sodium ascorbate, sugar andsodium tripolyphosphate are added with continued further blending for aperiod of two minutes producing a seemingly free-flowing powder mixturesuitable for both dry and wet curing of meat products when combined with8.33 grams sodium nitrite at the time of use.

EXAMPLE 3

A substantially dry free-flowing powder mixture is prepared containing553.3 grams sugar, 233.3 grams sodium tripolyphosphate, 36.7 gramssodium erythorbate, 33.3 grams alpha-tocopherol, 20 grams of the silicaflow agent and 24.7 grams lecithin.

The alpha-tocopherol, lecithin and silica additive agents are the sameas those employed in Example 1. The sugar constituent is a productcommercially available under the designation "Pure Fine GranulatedSugar" available from the Michigan Sugar Company. The sodiumtripolyphosphate additive comprises a commercially available productsold under the designation "Nutrifos, Light Density, Granular" availablefrom Monsanto Company. The sodium erythorbate constituent iscommercially available under the designation "Sodium Erythorbate,Granular" available from Pfizer, Inc.

The uniform mixture is prepared by the addition of the sugar, sodiumtripolyphosphate and sodium erythorbate to a ribbon blender in which themixture is heated to a moderate temperature of about 100° F. duringmixing. Thereafter, the tocopherol liquid additive is added duringcontinued further mixing and is blended for a period of two minutes. Thesilica flow agent is thereafter added followed by further mixing for aperiod of four minutes whereafter the lecithin powder is added followedby an additional one minute mixing. This procedure produces a seeminglydry free-flowing powder mixture of about 901 grams suitable for use asan ingredient for both dry and wet curing of meat products.

When used for meat curing this dry free-flowing powder totaling 901grams may typically be combined with 1000 grams of salt and 8.3 grams ofsodium nitrite and applied as a dry mixture on the exterior of meat. Themixture also disperses well in an aqueous media comprising 5,666 gramswater when 1000 grams of sodium chloride salt and 8.3 grams of sodiumnitrite are added to the same aqueous media containing 901 grams of themixture dispersed therein. The resulting dispersion is suitable forpumping in the wet meat curing process.

EXAMPLES 4 THROUGH 7

Substantially dry free-flowing powdered mixtures were prepared foraqueous incorporation in accordance with the formulation of ingredientsshown in Table 1, entitled "Composition of Curing Pickles for BaconProcessing".

Example 4 is a control to which no silica particulates,dl-alpha-tocopherol or lecithin were added. Sugar, salt, sodiumtripolyphosphate, sodium ascorbate and sodium nitrite were dissolved inwater.

In Example 5, a substantially dry free-flowing powdered mixture wasprepared containing 15 parts salt, 0.3 parts silicon dioxide and 0.5parts dl-alpha-tocopherol in the following manner. The sodium chloridefine flake salt is introduced into a ribbon blender at about 120° F. andto which the dl-alpha-tocopherol is added during continued furthermixing for a period of two minutes. Thereafter, the silica additive wasadded during continued further mixing for five minutes. To 71.725 partsof water were added and dissolved, 3.5 parts sodium tripolyphosphate,0.55 parts sodium ascorbate and 0.125 parts sodium nitrite. To thiscomposition was added 15.8 parts of the powdered mixture containingsalt, tocopherol and silicon dioxide. With mild agitation, a dispersionof good stability of dl-alpha-tocopherol was formed in the brine.

In Example 6, a substantially dry, free-flowing powdered mixture isprepared with 15 parts salt, 0.3 parts silicon dioxide, 0.5 partsdl-alpha-tocopherol and 1.0 parts lecithin. The mixture was prepared asin accordance with Example 5 except that the finely powdered lecithinadditive was added last with further mixing of one minute, with themixture at a temperature of less than about 120° F. To 70.725 parts ofwater were added and dissolved, 8.3 parts of sugar, 3.5 parts of sodiumtripolyphosphate, 0.55 parts sodium ascorbate and 0.25 parts sodiumnitrite. To this composition was added 16.8 parts of the mixture ofsalt, silicon dioxide, dl-alpha-tocopherol and lecithin. With mildagitation, a dispersion of excellent stability of dl-alpha-tocopherolwas formed in the brine.

In Example 7, a substantially dry, free-flowing powdered mixture isprepared by introducing 15 parts salt into a ribbon blender at about120° F. and to which 0.5 parts dl-alpha-tocopherol is added duringcontinued further mixing for a period of two minutes. Thereafter thesilica additive is added during continued further mixing for a fiveminute period. The finely powdered lecithin additive is thereafter addedduring further mixing of one minute with the mixture at a temperature ofless than about 120° F. The resultant mixture is substantially dry andfree-flowing with the constituents uniformly distributed. To thismixture was further added 8.3 parts of sugar, 3.5 parts sodiumtripolyphosphate, 0.55 parts sodium ascorbate and the mixture blended toresult in a substantially dry and free-flowing mixture with theconstituents uniformly distributed. To 70.725 parts of water was added29.15 parts of the above mixture. With mild agitation an excellentdispersion of dl-alpha-tocopherol was formed in the aqueous solution.Following this addition and establishment of a dl-alpha-tocopheroldispersion, 0.125 parts of sodium nitrite was added to the aqueoussolution and dissolved. The constituents employed in preparing Examples4 through 7 are the same as described in Example 3. The sodium ascorbateingredient was obtained from Pfizer, Inc.

The resultant curing pickles of Examples 4 through 7 were utilized forbacon processing in the following manner:

Fresh pork bellies were purchased soon after slaughter and stored for nomore than two days in a cooler at 2° C. The bellies were processed withcuring pickles according to the example treatments described in Table 1,using five randomly selected bellies for each treatment example. Thebellies were pumped to 110 percent of original weight with the exampletreatments shown in Table 1. The pumped pork bellies were equilibrated,after pumping, for 24 hours at 4° C. At the end of the curing period,the bellies were transferred to an Elek-Trol laboratory smokehouse(Drying Systems, Inc., Chicago, Ill.) and smoke cooked at a temperatureof 58° C. (dry bulb) for four hours, followed by three further hours ofsmoking at 52° C. (dry bulb) and ambient relative humidity. Smoke wasapplied through cooking using a midget size Mepaco smoke generator (MeatPackers Equipment Company, Oakland, Calif.) utilizing mixed hardwoodsawdust. The smoked bellies were transferred to a tempering cooler (-2°C.) where they were held overnight prior to slicing and packaging.

The five bellies per example treatment were sliced to approximately20-25 slices per pound or about 1/8 inch thickness and packaged in amanner similar to that found in retail packages. After each belly wassliced, it was packaged in 20 packages with the first slice going intothe first package, the second slice into the second package, the thirdslice into the third package and so on until the belly was completelypackaged. Thus, each of the 20 packages could be consideredrepresentative of an entire belly. Three packages randomly selected fromeach belly were analyzed for nitrosamines, while the remaining packageswere used for other determinations.

The effect of the treatments on N-nitrosamine inhibition are shown inTable 2. Example 5 was considered not an ideal formulation in that aslight surface film of tocopherol appeared after solution of the curingmix. However, it was not a gross phase break of the dispersion and themajority of tocopherol remained dispersed. Example treatments 6 and 7provided ideal dispersion of tocopherol with no detectable phase breakof tocopherol in the curing pickle. There were no significantdifferences in the inhibition of N-nitrosamines in either the friedbacon or the cooked-out fat between the example treatments 5, 6 and 7.In all cases, about 90 percent N-nitrosamine inhibition in fried baconwas attained for N-nitropyrrolidine (NPYR) and about 80 percent forN-nitrosodimethylamine (NDMA) in comparison to the control treatment ofExample 4.

                  TABLE 1                                                         ______________________________________                                        COMPOSITION OF CURING PICKLES                                                 FOR BACON PROCESSING, % BY WEIGHT                                                        EXAMPLE NO.                                                        INGREDIENTS  4        5        6      7                                       ______________________________________                                        Water        72.525   71.725   70.725 70.725                                  Salt         15.0     15.0     15.0   15.0                                    Sugar        8.30     8.30     8.30   8.30                                    Sodium Tripolyphos-                                                                        3.50     3.50     3.50   3.50                                    phate                                                                         Sodium Ascorbate                                                                           0.550    0.550    0.550  0.550                                   Sodium Nitrite                                                                             0.125    0.125    0.125  0.125                                   Silicon Dioxide                                                                            --       0.30     0.30   0.30                                    dl-alpha-tocopherol                                                                        --       0.50     0.50   0.50                                    Lecithin     --       --       1.00   1.00                                    ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________    N--NITROSAMINE LEVELS AND PERCENT INHIBITION OF N--NITROSAMINE                FORMATION IN BRINE-CURED BACON AND COOK-OUT FAT.sup.a                                Fried-Bacon                                                                             Cook-Out Fat                                                                           Fried-Bacon                                                                             Cook-Out Fat                              EXAMPLE                                                                              NPYR Inhibition                                                                         NPYR                                                                              Inhibition                                                                         NDMA Inhibition                                                                         NDMA Inhibition                           No.    μg/kg                                                                           %    μg/kg                                                                          %    μg/kg                                                                           %    μg/kg                                                                           %                                    __________________________________________________________________________    4      19.5 --   18.0                                                                              --   5.5  --   4.7  --                                          (14-27).sup.b                                                                           (13-28)  (4-6)     (3-6)                                     5      1.8  91   Trace                                                                             97   1.1  80   2.5  46                                          (1.1-2.9)          (ND-2.0)  (1.9-3.4)                                 6      2.5  87   Trace                                                                             97   1.3  76   2.5  46                                          (1.4-4.2)          (1.0-2.2) (1.1-3.2)                                 7      1.9  90   ND.sup.c                                                                          100  0.4  92   2.0  57                                          (1.6-2.5)          (ND-1.2)  (1.6-2.8)                                 __________________________________________________________________________     .sup.a Each value represents the average of three analyses of five bellie     per treatment.                                                                .sup.b Values in parentheses represent range of N--nitrosamines levels        obtained per treatment.                                                       .sup. c ND, not detected; limit of detection, 0.1 μg/kg.                   (microgram/kilogram).                                                    

EXAMPLE 8

A substantially dry free-flowing powder mixture is prepared containing1,000 grams fine flake salt, 20 grams dl-alpha-tocopherol, and 20 gramsof the silica flow agent; said agents are the same as those employed inExample 1. The uniform mixture is prepared by the addition of sodiumchloride salt at the temperature of about 120° F. to a ribbon blenderinto which the alpha-tocopherol is added during continued further mixingfor a period of two minutes. The silica flow agent is thereafter addedfollowed by further mixing for a period of about four minutes. To 2.6lbs. of this mixture were added, 0.83 lbs. sugar, 0.055 lbs. sodiumascorbate and 0.012 lbs. sodium nitrite. This combination was thenfurther thoroughly mixed by hand to achieve a final composition forutilization in a dry curing bacon application.

Pork bellies were purchased soon after slaughter and stored for no morethan two days in a cooler at 2° C. This mixture was applied to the porkbellies to achieve, on a pork belly fresh weight basis, the addition of2.5 percent salt, 0.83 percent sugar, 0.055 percent sodium ascorbate,0.012 percent sodium nitrite and 0.050 percent tocopherol. The mixturewas rubbed into the bellies and the bellies were placed in plastic bags(three bellies per bag) and held in the curing room at 2° C. The bellieswere inverted after five days to allow for good distribution of the curethroughout the bellies. At the end of the curing period, the bellieswere transferred to an Elek-Trol laboratory smokehouse (Drying Systems,Inc., Chicago, Ill.) and smoke-cooked at a temperature of 58° C. (drybulb) for four hours followed by three further hours of smoking at 52°C. (dry bulb) and ambient relative humidity. Smoke was appliedthroughout cooking using a midget size Mepaco smoke generator (MeatPackers Equipment Company, Oakland, Calif.) utilizing mixed hardwoodsawdust. The smoked bellies were transferred to a tempering cooler (-2°C.) where they were held overnight prior to slicing and packaging.

The six bellies per treatment were sliced 20-25 slices per pound orabout 1/8th inch thickness and packaged in a manner similar to retailpackages. After each belly was sliced, it was packaged in 20 packageswith the first slice going into the first package, the second slice intothe second package, the third slice into the third package and so on,until the belly was completely packaged. Thus, each of the 20 packagescould be representative of an entire belly. Six packages randomlyselected from each belly were analyzed for nitrosamines, while theremaining packages were used for other determinations. In addition tothis treatment, a similar treatment was conducted with a similar formulacomposition, except that tocopherol was not included. This controltreatment resulted in 42 micrograms per kilogram of NPYR in the friedbacon. The treatment containing tocopherol resulted in 1.5 microgramsper kilogram of NPYR, thus resulting in a 96 percent inhibition ofnitrosamine formation through the use of the mixture containingtocopherol.

While it will be apparent that the preferred embodiments of theinvention disclosed are well calculated to fulfill the objects abovestated, it will be appreciated that the invention is susceptible tomodification, variation and change without departing from the properscope or fair meaning of the subjoined claims.

What is claimed is:
 1. The method of forming a substantially stableaqueous curing brine suitable for wet curing or pumping of meat productsin which a controlled amount of dl-alpha-tocopherol is substantiallyuniformly dispersed therethrough comprising the steps of dissolving anddispersing in an aqueous medium a substantially uniform free-flowingparticulated composition consisting essentially of controlled amounts ofat least one water soluble finely particulated curing constituent,finely particulated water insoluble amorphous, tocopherol absorbentporous silica particles and dl-alpha-tocopherol distributedsubstantially uniformly on the particles of said curing constituent anddistributed on and absorbed in said silica particles.
 2. The method asdefined in claim 1 in which said composition further containsparticulated lecithin in an amount up to about 10 percent by weight. 3.The method as defined in claim 1 in which said curing constituentincludes particles selected from the group consisting of sodiumchloride, potassium chloride, sugar, phosphate salts, erythorbates,ascorbates, nitrites, nitrates and mixtures thereof.
 4. The method asdefined in claim 1 in which said particulated curing constituent isselected from the group consisting of sodium chloride, potassiumchloride and mixtures thereof.
 5. The method as defined in claim 1 inwhich the average particle size of said particulated curing constituentis less than about 500 microns.
 6. The method as defined in claim 1 inwhich the average particle size of said silica particles ranges fromabout 0.5 to about 9 microns.
 7. The method as defined in claim 1 inwhich said dl-alpha-tocopherol is present in an amount up to about 5percent by weight of said composition.
 8. The method as defined in claim1 in which said silica particles are present in an amount of at leastabout 0.33 part by weight per part by weight of saiddl-alpha-tocopherol.
 9. The method as defined in claim 1 in which saidcomposition further contains particulated lecithin in an amount of about1 to about 4 percent by weight of said composition.
 10. The method asdefined in claim 1 in which the average particle size of said curingconstituent ranges from about 100 to about 300 microns.
 11. The methodas defined in claim 1 in which the average particle size of said silicaparticles ranges from about 1.5 to about 7 microns.
 12. The method asdefined in claim 1 in which said silica particles are of an averageparticle size rangin; from about 0.5 to about 9 microns, said silicaparticles have a surface area of about 100 to about 500 square metersper gram, said silica particles have an oil absorption of about 100 toabout 350 cubic centimeters per 100 grams and said silica particles havean average pore diameter of about 20 to about 300 Angstroms.
 13. Themethod as defined in claim 1 in which said curing constituent comprisessodium chloride, potassium chloride or mixtures thereof present in anamount of about 94.85 percent by weight of said composition; saiddl-alpha-tocopherol is present in an amount of about 3.25 percent byweight, and said silica particles are present in an amount of about 1.9percent by weight of said composition.
 14. The method as defined inclaim 13 in which said composition further includes particulatedlecithin present in a weight ratio of lecithin to said silica particlesin an amount of about 6:1 to about 0.5:1.